TW200407668A - A chemical amplification type positive resist composition - Google Patents

Abstract

The present invention provides a resin which comprises a structural unit of the formula (I), wherein R1 represents alkylene having 1 to 4 carbon atoms, R2 represents alkyl having a to 4 carbon atoms, and R3 represents hydrogen or methyl, and also provides a chemical amplification type positive resist composition comprising a resin defined above and an acid generator.

Description

200407668 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to a chemically amplified positive photoresist composition, which can be used in fine semiconductor manufacturing processes. In addition, the present invention also provides a new type of resin material suitable for photoresist composition. [Previous Technology] Semiconductor microfabrication is usually implemented using lithography technology. According to the Rayleigh diffraction formula, the shorter the lithography exposure wavelength, the higher the resolution. In recent years, the lithography technology used in the production of semiconductor elements has been shortening the wavelength of the light source for exposure. For example, the wavelength of the g-line is 436 nm, the wavelength of the i-line is 365 nm, the wavelength of the KrF excimer laser is 248 nm, The molecular laser has a wavelength of 193 nm. Therefore, F2 excimer laser with a wavelength of only 157nm will be the next-generation exposure source with great application potential. In addition, extreme ultraviolet (EUV) with a wavelength of 13 nm or less is also considered to be a promising new generation of exposure sources after a 157 nm F2 laser. Since excimer lasers with shorter wavelengths (wavelengths less than g-line and i-line) have been used as exposure light sources, people have increasingly demanded photoresistance sensitivity. Recently, a type of light called a chemically amplified light The resist composition is used to improve the sensitivity of the photoresist. The photoresist can utilize a catalytic reaction of an acid generated by an acid generator such as a sulfcmium salt under a photosensitive condition to remove the protective group in the resin. In order to further reduce the exposure time, a chemically amplified photoresist composition is required to have a higher sensitivity than the conventional composition. [Summary of the Invention] 200407668 The object of the present invention is to provide a novel resin and a chemically amplified photoresist composition containing the aforementioned resin and an acid-producing source. The etchant is used in excimer laser lithography techniques such as KrF, ArF, etc., and shows excellent resistance to corrosion, especially greatly enhancing sensitivity. The resin and the large-scale photoresist composition containing the aforementioned resin and an acid generating source are as follows: (1) A resin containing a structural unit such as the chemical formula (I):

In the chemical formula (I), R1 represents an alkylene group containing 1 to 4 carbon atoms, R2 represents an alkyl group containing 1 to 4 carbon atoms, and R3 represents hydrogen or methyl. (2) The present invention also proposes a chemically amplified positive photoresist composition, which includes a resin component. This resin contains a structural unit of formula (I), which is insoluble or slightly soluble in an alkaline solution, but is insoluble with acid or acid. Soluble in alkaline solvents after source reaction. (3) The content of the structural unit according to the chemical formula (1) in the above point (2) is 10 to 80% (molar ratio) of the resin. (4) According to the composition described in the point (2) or (3), the resin structure contains not only the structural unit of the chemical formula (I), but also at least the following structural unit: 200,407,668 One: (meth) acrylic acid 3- The structural unit of 3-hydroxy-1-adamantyl (meth) acrylate is derived from 3,5-dihydroxy-1-Kanaoka! -l-adamantyl (meth) acrylate) is a structural unit derived from methacryloxy-τ · butyrolactone ((11 ^ 11) & (: 71〇71〇 \) ^ 7-131 ^ 1 < 〇 1 & (^ 〇1 ^) (a lactone may be substituted by a radical), a structural unit of the formula Ua) and (nb).

(I la) (I lb) R4 and R6 represent hydrogen or methyl, R5 and R7 represent methyl, and η represents an integer between 0 and 3. (5) According to any one of points (2) to (4), the resin component in the composition should further contain a structural unit derived from 2-norbornene and aliphatic unsaturated diacid anhydride. Structural units. (6) According to any one of the points (2) to (5), the acid-producing source in the composition should contain a ferrous salt of the chemical formula (Ha): 200407668

(Ilia) P1 ~ P3 represent hydrogen, hydroxyl, alkyl or alkoxy group containing 1 to 6 carbon atoms, respectively, and represent anions; or an iodine key salt represented by chemical formula (mb):

(Illb) P4 and P5 respectively represent hydrogen, a hydroxyl group, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, and ζ · represents an anion; or a sulfur key salt represented by a chemical formula (me): P6 \. p7 ^ S + ~ CH-C-P9 Z (nic) P6 and P7 respectively represent an alkyl group containing 1 to 6 carbon atoms or a cycloalkyl group containing 3 to 10 carbon atoms, or P6 and P7 are bonded to form Divalent aliphatic hydrocarbons of 3 to 7 carbon atoms, which are then cyclic with adjacent S +, and at least one of the divalent aliphatic hydrocarbons -CH2- can be -CO-,-200407668 〇- or- s- replaced. P8 represents a hydrogen atom, P9 represents an alkyl group containing 1 to 6 carbon atoms, a cycloalkyl group containing 3 to 10 carbon atoms, or a substituted aromatic compound, or P8 is bonded to P9, and then is adjacent to -CHCO -Formation of a 2-oxocycloalkyl group, Z. stands for the same meaning as above. (7) According to point (6), Z · in the composition represents an anion of the chemical formula (IV)

(IV) In the chemical formula (IV), Q1 to Q5 represent hydrogen, an alkyl or alkoxy group having 1 to 16 carbon atoms, halogen, an aryl group having 6 to 12 carbon atoms, and 7 to 12 carbons, respectively. Atomic aralkyl, nitrile, sulfide, hydroxyl, nitro, or group containing formula (I ') -COO-X-Gy' (I,) where X represents an alkylene group and an alkylene group At least one -CH2- in the group may be substituted by -0- or -S-, and Cy1 represents an alicyclic hydroxyl group having 3 to 20 carbon atoms. (8) According to any of the points (2) to (7), the content of the resin in the composition accounts for 80 to 99.9% of the total weight of the resin and the acid generating source, and the content of the acid generating source accounts for 0.1 to 20% of the total weight . -10- 200407668 (9) According to any one of points (2) to (8), the composition also contains {a nitrogen-containing organic compound that is a quencher. (10) According to item (9), the content of the nitrogen-containing organic compound in the composition is 0.001 to 1% of the total resin weight. In order to make the above and other objects, features, and advantages of the present invention more comprehensible, a preferred embodiment is given below and described in detail with reference to the accompanying drawings. [Embodiment] The photoresist composition of the present invention includes: (1) a resin containing a structural unit such as chemical formula (I):

In the chemical formula (I), R1 represents an alkylene group containing 1 to 4 carbon atoms' R2 represents an alkyl group containing 1 to 4 carbon atoms, and R3 represents hydrogen or methyl. The resin itself is insoluble or slightly soluble in an alkaline solution 'but is soluble in an alkaline solvent after reacting with an acid or an acid generating source. (Hereinafter referred to as "resin compound") and (2) an acid generating source. In the formula (I), 'Rl represents an alkylene group containing 1 to 4 carbon atoms, including methylene, vinyl, propenyl, isopropenyl, butenyl, chloro-methyl 200407668 vinyl, 2- Methyl vinyl, 1,2-dimethylethylene, 1-ethylethylene, 2-ethylethylene, 1-methylpropylene, 2-methylpropylene, 3-methylpropylene, acetal, Propyl, butylene, etc. R2 represents an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 2-butyl, tert-butyl and the like. R3 represents hydrogen or methyl. The resin compound contains structural units such as formula (I) and other structural units, as long as the resin itself is insoluble or slightly soluble in an alkaline solution, but is soluble in an alkaline solvent after reacting with an acid or an acid generating source. The resin compound can be prepared by polymerizing a monomer represented by the chemical formula (I '),

Wherein R1, R2, and R3 have the same meanings as those described in the chemical formula (I). Furthermore, it can also be prepared by copolymerization of a monomer containing a chemical formula (I '). The monomer represented by the chemical formula (I ') can be prepared by the following method: First, an alkoxy halohydrocarbon (halogen may be Cl, Br, I) is reacted with metal lithium or magnesium to form an alkylating agent, and then 2 -Amantadone reacts with the obtained alkylating reagent to obtain 2- (4-methoxybutyl) -2-adamantanol, and finally 2- (4-methoxybutyl) -2-adamantanol and methyl The target monomer is obtained by reacting acryloyl chloride in 1-methylpyridine-12-200407668. The monomers represented by the chemical formula (I ') include:

In addition to the monomer represented by the chemical formula (I '), the resin compound can be obtained by copolymerizing other monomers containing an acid-labile group. This acid-labile group can be selected from a variety of protecting groups which have the ability to inhibit the resin from dissolving in an alkaline aqueous solution. Such a group may be tert-butyl; a tetracarbon atom adjacent to an oxygen atom, such as terbutoxycarbonyl, terbutoxycarbonylmethyl, etc .; a group with an acetyl group such as tetra-13- 200407668 hydrogen- 2-pyranyl, tetrahydro-2-furanyl, 1-ethoxyethyl, 1- (2-methylpropoxy) ethyl, 1- (2-methoxyethoxy) ethyl , 1- (2-acetoxyethoxy) ethyl, [2- (1-adamantyloxy) ethoxy] ethyl, 1-PO-adamantylcarbonyloxy) ethoxy] ethyl Etc., groups with alicyclic moieties such as 3-oxetanyl, 4-methyltetrahydro-2-pyran-4-yl (introduced from mevalonolactone), 2-methyl- 2-adamantyl, 2-ethyl-2-adamantyl and the like. The hydrogen atom on the phenolic hydroxyl group or carboxyl group in the resin may be replaced by an acid-labile group, and the acid-labile group may be obtained by a conventional substitution introduction reaction. The resin compound can also be obtained by copolymerizing an unsaturated compound containing an acid-labile group with a monomer represented by the chemical formula (I '). The resin compound may also contain other structural units which do not dissociate or are not easily dissociated after reacting with an acid. Such structural units can be derived from monomeric structural units containing a reactive carboxyl group such as acrylic acid and methacrylic acid, fatty unsaturated diacid anhydrides such as maleic anhydride and itaconic anhydride structural units, norbornyl structural units, (meth) acrylonitrile Structural units, and other (meth) acrylate structural units. For KrF light sources, since there is no light absorption problem, this structural unit can also be derived from hydroxystyrene. It should be noted that in consideration of the adhesion of the photoresist to the substrate, in addition to the structural unit represented by the chemical formula (I '), the resin compound also contains at least one structural unit derived from (meth) acrylic acid 3-hydroxy-1 -Adamantyl ester, 3,5-dihydroxy-1-adamantyl (meth) acrylate, (meth) acryloyloxy-T-butyrolactone, chemical formula (na) or chemical formula (nb). 200407668

(I la)

In the chemical formula (Ila) and the chemical formula (nb), R4 and R6 respectively represent a 7K hydrogen atom or a methyl group, R5 and R7 represent a methyl group, and η represents an integer between 0 and 3. 3-Hydroxy-1-adamantyl (meth) acrylate and 3,5-dihydroxy-1-adamantyl (meth) acrylic acid can be reacted with (meth) acrylic acid or its acyl through the corresponding hydroxyadamantane It can be obtained by reaction of halogen, and it is also available on the market. In addition, (meth) acryloyloxy-r-butyrolactone can be obtained by reacting acrylic acid or methacrylic acid or bromo-r-butyrolactone (lactone may be substituted by alkyl group), or by α or dot-hydroxy-r-butyrolactone is obtained by reacting with an acryl halide or a methacryloyl halide. Monomers can be used to prepare structural units of formula (Πa) and structural units of formula (nb). Some examples are listed below, such as (cyclo) lactone (meth) acrylates with hydroxyl groups, their mixtures and analog. These esters can be obtained by reacting the corresponding hydroxyl lactones with methacrylic acid. For detailed preparation methods, please refer to Japanese Patent JP2000-26446-A 〇 -15- 200407668

When the resin compound contains the following structural units, such as 3-hydroxy-1-adamantyl (meth) acrylate, 3,5-dihydroxy_1-adamantyl (meth) acrylate, (meth) acrylic acid When dilute acyloxy-butyrolactone and structural units of chemical formula (Ha) or chemical formula (nb), not only the adhesion between the photoresist and the substrate is strengthened, but also the resolution of the photoresist is greatly improved. (Meth) acryloyloxy-r-butyrolactone 'as used herein includes: α-acryloyloxy-r-butyrolactone, α-methacryloyloxy-r-butyrolactone, α -Acryloyloxy- / 5, / 5-dimethyl-r-butyrolactone, methylpropanoyloxy-n, / 3 dimethyl1-butyrolactone, α-acryloyloxy-α -Methyl-r-butyrolactone, α-methylpropanyloxy-α-methyl-r-butyrolactone, / 3-acryloyloxy-r-butyrolactone, methacrylic acid Acyloxybutyrolactone, cold-methacryloyloxy-α-methylbutyrolactone, and the like. When the resin contains a structural unit derived from 2-norbornene, since the alicyclic group appears directly on the main chain, the resin exhibits a stable structure and excellent dry-saturation resistance. The structural unit derived from 2-norbornene can be introduced into the main chain by radical (initiated) polymerization reaction using 2-norbornene's unsaturated fatty diacid anhydrides such as maleic anhydride and itaconic anhydride, and then by opening the two The bond 'forms a structural unit of 2-norbornene. This structural unit can be expressed by the formula 200407668 (V). The structural single ΐ derived from maleic anhydride and itaconic anhydride is formed by opening their double bonds, respectively, which can be expressed as chemical formula (VI)

In the chemical formula (V), R8 and R9 represent hydrogen, respectively, a radical or hydroxyl radical containing 1 to 3 carbon atoms, a radical, a cyano group, a group (z represents an alcohol part), or R8 and R9 are bonded. An anhydride group -C (= 0) 0C (= 0)-is formed. The radicals in R8 and R9 include methyl, ethyl, propyl, and isopropyl, and the alkyl groups include methylol, 2-hydroxyethyl, and the like. The -COOZ group in R8 and R9 is an ester group generated from a carboxyl group, and z represents a part of an alcohol, for example, an optionally substituted alkyl group containing 1 to 8 carbon atoms, including 2-oxoxuracil-3-yl or 4-Alkyl and the like 'substituted alkyl, substituted hydroxyl, substituted cycloalkane and the like. Typical examples of -COZ include methyl carboxylate, ethyl carboxylate, ethyl 2-hydroxycarboxylate, tert-butyl carboxylate, carboxylic acid (2-oxoxuracil-3 -Yl) ester group 'carboxylic acid (2-oxoxuracil-4-yl) ester group, carboxylic acid (1,1,2-trimethylpropyl) ester group, carboxylic acid (bucyclohexyl-1- Methyl ethyl) acetic acid, carboxylic acid [1- (4-methylcyclohexyl) -1-methylethyl] ester, carboxylic acid [1- (1-adamantylcyclohexyl) -1-methylethyl ] Ester group and so on. The monomers used to prepare the structural unit of formula (V) include the following: -17- 200407668 2-norbornene 2-hydroxy-5-norbornene 5-norbornene-2-carboxylic acid 5-norbornene-2- Methyl formate 5-norbornene-2-carboxylic acid tert-butyl ester 5-norbornene-2-carboxylic acid (1-cyclohexane-1-methyl) ethyl ester 5-norbornene-2-carboxylic acid [1 -(4-methylcyclohexyl) -1-methyl] ethyl 5-norbornene-2-carboxylic acid [1- (4 · hydroxycyclohexyl) -1-methyl] ethyl 5-norbornene- 2-carboxylic acid [1-methyl-1- (4-oxocyclohexyl)] ethyl ester 5-norbornene-2-carboxylic acid [1- (1-adamantyl) -1-methyl] ethyl ester 5 -Norbornene-2-carboxylic acid (1-methyl) cyclohexyl 5-norbornene-2-carboxylic acid (2-methyl) -2adamantyl ester 5-norbornene-2-carboxylic acid (2-ethyl Base) -2 adamantyl ester 5-norbornene-2-carboxylic acid (2-hydroxy) ethyl ester 5-norbornene-2-methanol 5-norbornene-2,3-dicarboxylic anhydride and the like. The content of the structural unit of the chemical formula (I) in the resin compound is generally 10 to 80% (molar content) of the total structural unit amount, preferably 15 to 80%. The optimal content will be based on the type of light source exposed, acid-not Factors such as stabilizing groups. In addition to the structural unit of formula (I), when the resin compound contains other structural units that do not dissociate or are not easily dissociated after reacting with an acid, such as 3-hydroxy-1-adamantyl (meth) acrylate, (methyl ) 3,5-dihydroxy-1-adamantyl acrylate, α- (meth) acryloyloxy-r-butane-18-200407668 ester, cold- (meth) acryloyloxy-r-butane Lactone, chemical formula (π a) or chemical formula (nb), hydroxystyrene, chemical formula (ν), (νι), (νπ), etc., the content of these structural units preferably accounts for 20 ~ 90 ° of all structural units of the resin / . (Molar content). When 2-norbornene and unsaturated fatty dianhydride are used as comonomers, an appropriate excess of monomers should be added depending on the ease of polymerization. Another compound in the positive photoresist composition, an acid-producing source, is a compound capable of decomposing to generate an acid under the action of radiation such as light or an electron beam. The acid produced by the acid generating source acts on the resin and can remove acid-labile groups from the resin. The acid-producing source in the resin composition of the present invention includes 7K ferric iron salt as shown in chemical formula (ma): p2.

Among them, P1 to P3 respectively represent hydrogen, a hydroxyl group, an alkyl group or an alkoxy group containing 1 to 6 carbon atoms, and Z · represents a sulfate salt; or an iodine key salt represented by the chemical formula (mb):

Among them, P4 and P5 respectively represent hydrogen, a hydroxyl group, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, and Z · represents a sulfate salt; -19- 200407668 or a sulfur key salt represented by chemical formula (me): ρβ ^ 〇7 ^ -ch-c-p9 Z (me) p7〆 > where P6 and P7 respectively represent an alkyl group containing 1 to 6 carbon atoms or a cycloalkyl group containing 3 to 10 carbon atoms, or P6 and P7 Bonding occurs to form a divalent aliphatic hydrocarbon containing 3 to 7 carbon atoms, which then forms a ring with adjacent S +, and at least one of the divalent aliphatic hydrocarbons -CH2- can be replaced by -CO- , -0- or -S- substituted. P8 represents a hydrogen atom, P9 represents an alkyl group containing 1 to 6 carbon atoms, a cycloalkyl group containing 3 to 10 carbon atoms, or a substituted aromatic compound, or P8 is bonded to P9, and then is adjacent to -CHCO -Formation of a 2-oxocycloalkyl group, Z. stands for sulfate ion. The alkyl group represented by P1 to P5 may be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, a hexyl group, or the like; the alkoxy group may be a methoxy group, an ethoxy group, Propoxy, isopropoxy, butoxy, tert-butoxy and the like. The alkyl groups represented by P6, P7, and P9 include methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, etc .; cycloalkyl includes cyclopropyl, cyclobutyl, Cyclopentyl, cyclohexyl, cycloheptyl, etc .; cyclic groups formed by divalent aliphatic hydrocarbons (P6 and P7 are bonded) and adjacent S + include: cyclopentyl, tetramethylenefluorenyl , Oxodivinyl and the like, the aromatic groups represented by P9 include phenyl, tolyl, xylyl, naphthyl and the like. 2-oxocycloalkyl (P8 and P9 are bonded and then formed with the adjacent -CHCO-) There are 2-oxocyclohexyl, 2-oxocyclopentyl and so on. Z · represents an anion. Such anions may include alkanesulfonate, haloalkanesulfonate, halophosphate, haloborate, haloantimonate, and anion represented by the formula (IV):

(IV) where Q1 to Q5 represent an alkyl group containing 1 to 15 carbon atoms, an alkoxy group containing 1 to 16 carbon atoms, a halogen, an aryl group containing 6 to 12 carbon atoms, and 7 to 12 Aralkyl, nitrile, sulfide, hydroxyl, nitro, or groups containing chemical formula (IV ') — COO—X ~ Cy1 (IV,) where X represents an alkylene group, and At least one -ch2- in the alkyl group may be substituted by -0-, and Cy1 represents an alicyclic hydroxyl group containing 3 to 20 carbon atoms. Branched alkyl groups containing 1 to 15 carbon atoms, including methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecane Group, hexadecyl and the like. Alkoxy groups containing 1 to 16 carbon atoms, including methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, pentyloxy, hexyloxy, octyloxy , Decyloxy, dodecyloxy, hexadecyloxy, etc. Halogen includes fluorine, chlorine, bromine, iodine and the like. Aryl groups containing 6 to 12 carbon atoms include phenyl, tolyl, methoxyphenyl, naphthyl and the like. Aralkyl groups containing 7 to 12 carbon atoms include benzyl, chlorobenzyl, methoxybenzyl and the like. -21-200407668 When the chemical formula (I ') contains two or more groups of Q1 to Q5, the groups of the formula (I') may be the same or different. X represents the following groups: —CH2- (a -1) -CH2-CH2 ·-* (a -2) —CH2-CH2-CH2- (a -3) —CH2-CH2-CH2-CH2- (a W ) --CH2-CH2-CH2-CH2-CH2- (a -5)

—CH2-CH2 * CH2 * CH2CHrCH2 · (a -6) —CH2-CH2-CH2-CH2CH2-CH2-CH2-CH2- (a-7) —CH2O — (3 -8) —CH2-〇—CH2- ( a -9) -CH2-〇—CH2-CH2- (a-10) —CHz-CHaO—〇H2-CH2- (a -11) —CH2 ~ S— · 12) —ch2-s-Civ (a · 13) —CH2-S—CH2-CH2- (a -14)

-CH2 ~ OH2 " S-CH2 * CH2- (q-15) X is preferably a group represented by the above (a-1) to (a-7). Cy1 includes the following groups: -22- 200407668 -〇 0 > 1) -〇 (b-2) (t > 4)

(S > 11) ~ C〇 (Bu 21) -φ), 22 |

〇 _ x〇 -ib_s) -〇〇-OD φ-14) (b-15)

-O Ms1D (Negotiation (ί > 45)

(b-16)

(Ii) Among them, Cy1 is preferably cyclohexyl (b-4), 2-norbornyl (b-21), 1-adamantyl (b-24), and 2-adamantyl (b-23) ). The cations in the formula (ma), (mb) or (me) include the following groups: -23- 200407668

-24 200407668

6¾ 6 ^ 〇 ^ M〇4-O ^ f 〇 ^ ~ ^ 〇〇 ^ ~ 〇- °--ο ^ Ο- ^ Ό · ^ 0 * · The anion in Chemical Formula (IV) includes the following groups: -25 -200407668

-26- 200407668

-27- 200407668

28- 200407668

200407668

In addition to the anion represented by the chemical formula (IV), the anion includes trifluoromethanesulfonate, fluorobutylsulfonate, fluorooctylsulfonate, hexafluoroantimonate, tetrafluoroborate, hexafluorophosphate, and the like. The source of acid in the photoresist composition can be obtained from commercial sources or can be prepared by conventional methods. For example, when Z represents an anion represented by the chemical formula (IV), sulfur key salts (nia), iodonium salts (mb), and sulfur key salts (IIC) can be prepared by the following conventional methods. -30- 200407668 For example, sulfur gun salt (ma) can be prepared by reacting the corresponding triphenyl bromide mirror with the target silver salt of sulfonate; or described by Japanese patent ρ-1108 ·· 311018-A Prepared by the method ... First, the aryl-form reagent is reacted with thionyl chloride, and the obtained product is then reacted with a trialkyl halide to obtain a diaryl hafnium halide, and then it is mixed with a silver sulfonate salt having the same sulfonate anion structure. Reaction to obtain the target product. The sulfonate in formula (ma) (Pl, P2 or P3 represents a hydroxyl group) can be determined by the method described in Japanese Patent JP_H08-157451-A through the triphenyl mirror salt containing tert-butanol ether on the benzene ring and the same It is prepared by reacting sulfonate with sulfonate anion structure. Sulfur key salts (me) can be prepared by referring to the polymer chemistry album of the journal J. poiymer Science, vol. 17, pages 2877-2892 (1979), prepared by J.V. Crivello et al. First, the / 5-haloketone is reacted with the corresponding sulfide to obtain the corresponding hafnium halide, and then the hafnium halide is reacted with the corresponding sulfonic acid or sulfonate to obtain the designed target product. The iodine key salt (Mb) can be prepared according to the method described in J. Am. Chem. Soc., Vol. 81, page 342 (1959), that is, by reacting iodine sulfate with the corresponding aryl compound, and then adding The sulfonic acid with the same anionic structure of the iodine key salt can be reacted to obtain the product. It can also be prepared by adding iodine and trifluoroacetic acid to a mixture containing acetic anhydride and fuming nitric acid. The resulting mixture is reacted with the corresponding aryl compound, and finally a sulfonic acid containing the same anionic structure of the iodine key salt is added thereto to obtain the target product; the aryl compound containing the It is prepared by gradually adding sulfuric acid dropwise to a mixture of a base compound, acetic anhydride and potassium iodate, and then adding a dangling-31-200407668 acid containing the same anionic structure of the iodine key salt to it. In the photoresist composition system of the present invention, the deterioration of the material properties is mainly caused by the diffusion of the acid in the photoresist after exposure, which results in the inactivation of the acid. Therefore, by adding an organic basic compound as an acid quencher, the acid diffusion can be suppressed. A nitrogen-containing organic basic compound is an ideal choice. For example, an amine containing the following structure is a preferred nitrogen-containing organic basic compound.

In formula (3), T12 and T13 represent hydrogen, alkyl, cycloalkyl or aryl, respectively. The alkyl group preferably contains 1 to 6 carbon atoms, the cycloalkyl group preferably contains 5 to 10 carbon atoms, and the aryl group preferably has 6 to 10 carbon atoms. In addition, at least one hydrogen atom in an alkyl group, cycloalkyl group, or aryl group can be substituted by a hydroxyl group, an amine group, or an alkoxy group containing 1 to 6 carbon atoms, and at least one hydrogen atom in the amine group can be replaced by Alkyl substitution with 1 to 4 carbons. -32- 200407668 T14, T15 and T16 represent hydrogen, alkyl, cycloalkyl, aryl or alkoxy, respectively. The alkyl group preferably contains 1 to 6 carbon atoms, the cycloalkyl group preferably contains 5 to 10 carbon atoms, the aryl group preferably has 6 to 10 carbon atoms, and the alkoxy group preferably contains 1 to 6 carbon atoms. In addition, at least one hydrogen atom in the alkyl, cycloalkyl, aryl, or alkoxy group can be substituted by a hydroxyl group, an amine group, or an alkoxy group containing 1 to 6 carbon atoms, respectively. One hydrogen may be substituted by an alkyl group containing 1 to 4 carbons. T17 represents alkyl or cycloalkyl. The alkyl group preferably contains 1 to 6 carbon atoms, and the cycloalkyl group preferably contains 5 to 10 carbon atoms. In addition, at least one hydrogen atom in each of the alkyl group and the cycloalkyl group can be substituted by a hydroxyl group, an amine group, or an alkoxy group containing 1 to 6 carbon atoms, and at least one hydrogen atom in the amine group can be substituted by 1 to Substitution of 4 carbons. T18 represents alkyl, cycloalkyl or aryl. The alkyl group preferably contains 1 to 6 carbon atoms, the cycloalkyl group preferably contains 5 to 10 carbon atoms, and the aryl group preferably has 6 to 10 carbon atoms. In addition, at least one hydrogen atom in an alkyl group, cycloalkyl group, or aryl group can be substituted by a hydroxyl group, an amine group, or an alkoxy group containing 1 to 6 carbon atoms, and at least one hydrogen atom in the amine group can be replaced by Alkyl substitution with 1 to 4 carbons. However, it should be noted that T12 and T13 in formula (3) cannot be hydrogen. The A atom in the formula (3) represents an alkylene group, a carbonyl group, an amine group, a sulfide or a disulfide. Among them, the alkylene group is preferably an alkylene group having 2 to 6 carbons. It should be added that the carbon chains in T12 ~ T18 can be straight or branched. -33- 200407668 T19, T2 (), and T21 represent hydrogen, an alkyl group containing 1 to 6 carbons, an amine alkyl group, and a hydroxyalkyl group, respectively, or a substituted (unsubstituted) aryl group containing 6 to 20 carbon atoms Among them, T19 may also be bonded to T2 °, and the alkylene group formed with the adjacent amide group (CO-N-) forms a cyclic lactam. Such compounds include hexylamine, heptylamine, octylamine, nonylamine, decylamine, aniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, 1- or 2-naphthylaniline, ethylene Methyl diamide, tetra-substituted methylethylene diamide, hexa-substituted methyl ethylene diamide, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino- 3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, dibutylamine, dipentylamine, dihexylamine, diheptylamine , Dioctylamine, dinonylamine, didecylamine, N-methylaniline, piperidine, diphenylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, dihexylamine, diheptyl Amine, dioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyl Dioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine Ethylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylmethylamine, tris [2- (2-methylethyl ether) Ethyl] amine, triisopropylamine, N, N-dimethylamine, 2,6-isopropylamine, imidazole, pyridine, 4-methylpyridine, 4-methylimidazole, dipyrimidine, 2- 2'-dipyridylamine, bis-di-pyridone, 1,2-bis- (di-pyridine) ethane, 1,2-bis- (tetra-pyridine) ethane, 1,3-bis · (tetra -Pyridine) propane, 1,2-bis- (di-pyridine) ethylene, 1,2-bis- (tetra-pyridine) ethylene, 1,2-bis- (di-pyridyloxy) ethane, 4,4 ' -Dipyridine sulfide, 4,4'-dipyridine disulfide, 2,2'-dipyridylmethylamine, 3,3'-dipyridylmethylamine, tetramethylhydroxyammonium, tetraisopropyl-34 -200407668 hydroxyammonium, tetrabutylhydroxyammonium, tetra-n-hexylhydroxyammonium, tetra-n-heptylhydroxyammonium, phenyltrimethylhydroxyammonium, 3-trifluoromethylphenyltrimethylhydroxyammonium , (2-hydroxyethyl) trimethylhydroxyammonium (commonly known as choline), N-methylpyrazole, dimethylimidazole, and so on. In addition, a hindered amine compound containing a piperidine skeleton disclosed in Japanese Patent JP-A-H1 1-52575 can also be used as a quencher. In the photoresist composition of the present invention, the resin content accounts for about 80 to 99.9 WT.% Of the total solid weight, and the optimal content of the acid source is 0.1 to 20% by weight of the resin. When an organic city quencher is contained, the content of the quencher is 0.001 to 1% by weight of the resin, and the optimum content is 0.01 to 1%. Within the scope of the present invention, the photoresist may also contain small amounts of other various additives, such as photosensitizers, barrier solvents, other resins, surfactants, stabilizers and dyes. This composition is usually prepared by dissolving various components in a solvent, so the photoresist exists in a liquid form. In use, a conventional spin coating method is used to coat a photoresist on a substrate such as a silicon wafer. The content of the solvent should be moderate. It is necessary to ensure that the solid components in the photoresist are completely dissolved, and the drying rate of the solvent is required to obtain a uniform, smooth and flat coating after the solvent has completely evaporated. In the present invention, the total solid content refers to the total amount of substances other than the solvent. The solvent satisfying the above conditions may include a glycol ether ester compound such as ethyl acetate cellulose solvent, methyl acetate cellulose solvent, propylene glycol monomethyl ether acetate; an ester compound such as ethyl lactate, butyl lactate, Amyl lactate, ethyl pyruvate, etc .; Ketone compounds, such as acetone, methyl isobutyl-35-200407668 based ketones, 2-heptanone, cycloheptanone; cyclic (like) esters, such as r-butyrolactone, etc. . These solvents can be used alone or in combination. After the photoresist is coated on the substrate and dried and exposed, an image is formed on the substrate, and further heat treatment is performed to promote a deblocking reaction, and then developed with an alkaline developer. The basic developer used here may be any of the ones mentioned in the present invention, among which tetramethylhydroxylamine and (2-hydroxyethyl) trimethylhydroxyammonium (commonly known as choline) are most commonly used. The above-disclosed specification discusses the core part of the present invention and the protection scope of the present invention in detail, but the scope of protection of the present invention is not only the above content, but also includes all related or equivalent content. The following examples are further explanations of the content of this party, but at the same time it should be pointed out that the content of the present invention is not limited to the examples. In the following examples, all raw material ingredients are by weight unless otherwise specified. Product weight The average molecular weight was determined by gel permeation chromatography (calibrator is polystyrene). Synthesis Example 1 of Acid Production Source (Synthesis of Acid Production Source B1) 20 parts of 2,4,6-triisopropyl-3-nitrobenzenesulfonic acid, 80 parts of acetonitrile and 40 parts of acetone were added to the flask at room temperature After stirring for 16 hours, 7.46 parts of silver oxide was added to the mixture, and stirring was continued at room temperature for 16 hours. After filtration and concentration, 23.68 parts of 2,4,6-triisopropylnitrobenzene were obtained. Silver sulfonate. In another flask, 20 parts of silver 2,4,6-triisopropyl-3-nitrobenzenesulfonate and 185.35 parts of methanol prepared above were added, and 53 parts of hydroiodic acid p --- A mixture of toluyl biphenylsulfide and 185.35 parts of methanol-36-200407668 was stirred at room temperature for 16 hours. It was filtered, and the filtrate was concentrated, and 300 parts of chloroform was added to the concentrated product, followed by washing three times with 75 parts of deionized water. After that, the organic layer was taken out and concentrated. To the concentrated product was further added tert-butyl methyl ester, and 22.07 parts of the intended product was obtained after crystallization. The product of this purpose is called 2,4,6-triisopropyl-3-nitro-benzenesulfonic acid (4-methyl) phenyldiphenylsulfide salt. After NMR analysis, the structure is:

iH-NMR (dimethyl sulfenyl-d6, internal standard substance: tetramethylsilane): 5 (ppm) 1.10-1.19 (m, 18H); 2.44 (s, 3H); 2.46-3.56 (m, lH) ; 4.61-4.71 (m, 1H); 4.972 (br, 1H); 7.32 (s, 1H); 7.59-7.62 (m, 2H); 7.74-7.88 (m, 12H) Acid Production Source Synthesis Example 2 (Acid Production Synthesis of source B2) 'Add 6 parts of 5-thioisophthalic acid and 50 parts of cyclohexanol to the flask and stir at 135 to 14 (TC for 9 hours. After cooling, then add 50 parts to this mixture A mixture of dimethylformate, 10 parts of methanol and 200 parts of η-hexane, stirred and left for a while to separate the layers. The lower layer was separated and washed twice with η-hexane. Then the upper layer and the two washed The mixture of the lower layer was concentrated by evaporation. 30 parts of silver oxide was added to the concentrated mixture, and the mixture was stirred at room temperature for 16 hours. It was filtered, and the filtrate was concentrated, and 8.67 parts of hydrogen iodide was added to the concentrated product. A mixture of p-tolyl acid 37-200407668 biphenylsulfide salt and 86.7 parts of methanol, and stirred at room temperature for 16 hours. After filtration, 200 parts of ethyl acetate was added to the filter, and 100 parts of ion Wash five times with water. Take out the organic layer, concentrate, add 200 parts of η-hexane to the concentrated product, and concentrate. Repeat the washing and concentration twice. After the concentrate is washed with 200 parts of η-hexane, wash, Concentrated and filtered to obtain 6.24 parts of pale yellow crystalline product. After NMR and mass spectrometry analysis, the crystalline compound has the following structure:

iH-NMR (chloromethane_d, internal standard substance: tetramethylsilane): 6 (ppm) 0.94-1.00 (m, 4H); 1.14-1.26 (m, 6H); 1.41-1.44 (m, 2H); 1.62-1.76 (m, 14H); 2.44 (s, 3H); 4.32-4.34 (t, 4H); 7.46-7.47 (d, 2H); 7.65-7.77 (m, 12H); 8.61 (s, 1H); 8.77 (S, 2H) MS (ESI (+) spectrum): M + 277.2 MS (ESI (-) spectrum): M- 465.2 Resin Synthesis Example 1 (Synthesis of A1 Resin) 9.18 g of the monomer represented by the chemical formula () 3.33g of 5-methacryloyloxy-2,6 · norbornenolide and 4.73g of «· (meth) acryloyloxy r -butyrolactone monomer raw material, at a molar ratio of 50: 25: 25 After the proportions are weighed and mixed 'Place in the flask. Methyl isobutyl ketone was added twice the weight of all monomers, mixed well and heated to 80 ° C, and then -38- 200407668 azobisisobutyronitrile initiator (its content 3% of the molar mass of all monomers), and heated to 85 ° C for about 5 hours. Then, a large amount of methanol was added to the reaction solution to generate crystals, and this was repeated three times to purify the crystalline product. Drying gave 11.3 g of copolymerized product. After analysis, the reaction yield was 65.6%, and the weight average molecular weight of the polymerization product was 5,500. The molecular weight distribution was 1.79. This copolymer is called resin A1. Resin Synthesis Example 1 (Synthesis of A2 Resin) 10.0 g of the monomer represented by the chemical formula (VEI) and 7.25 g of 5-methacryloyloxy_2,6-norbornenolide monomer raw materials were prepared in order to 50:50 molar ratio was weighed and mixed and placed in a flask. Methyl isobutyl ketone was added twice as much as the weight of all monomers, mixed well and heated to 80 ° C, and then azobisisobutyronitrile initiator (the content of which was all 3% of the molar mass), the subsequent reaction and post-treatment were operated according to the conditions of Synthesis Example 1. Finally, 11.5 g of copolymerized product was obtained. After analysis, the reaction yield was 66.7%, the weight average molecular weight of the polymerization product was 19,000, and the molecular weight distribution was 2.02. This copolymer is called resin A2. Resin Synthesis Example 3 (Synthesis of A3 Resin) 9.18 g of the monomer represented by the chemical formula (VI), 2.22 g of 3-hydroxy-1-adamantyl methacrylate and 12.48 g of 5-methacryloyloxy-2, 6-norbornenolide was weighed and mixed in a ratio of 30:10:60 molar ratio, and then placed in a flask. Methyl isobutyl ketone was added twice as much as the weight of all monomers, thoroughly mixed and heated to 8 CTC, and then azobisisobutyronitrile initiator (the content of which is the molar mass of all monomers) 3%), the subsequent reactions and post-treatments were performed according to the conditions of Synthesis Example 1. Finally, 21. 4 g of -39- 200407668 copolymerized product was obtained. After analysis, the reaction yield was 89.6%, the weight average molecular weight of the polymerization product was 7,300, and the molecular weight distribution was 1.77. This copolymer is called resin A3. Resin Synthesis Example 4 (Synthesis of A4 Resin) 2-ethyl-2-adamantyl methacrylate, 5-methacryloyloxy-2,6-norbornenolactone, and methyl (meth) acryloyl The oxybutyrolactone monomer raw material is weighed and mixed at a ratio of 2: 1: 1 (or ll.lg: 5.0g: 3.8g), and 50 g of a 4-dioxane product is added thereto. Into a solution. Then, 0.3 g of azobisisobutyronitrile initiator was added to the solution, and the mixture was thoroughly mixed and heated to 85 ° C for about 5 hours. Then, a large amount of? -Hexane was added to the reaction solution to generate a precipitate, and this was repeated three times to purify the precipitated product. Finally, a copolymer having a weight average molecular weight of 9,100 and a molecular weight distribution of 1.72 was obtained. This copolymer is called resin A4. Resin Synthesis Example 5 (Synthesis of Α5 Resin) 2-ethyl-2-adamantyl methacrylate and 5-methacryloyloxy-2,6-norbornanoate (5-methacryloyloxy-2,6 -norbornanecarolactone) monomer material, weighed and mixed at a 1: 1 molar ratio (or 12.42 gzll.lg), and then added 47 g of 1,4-dioxane to the solution. Then add azobisisobutyronitrile initiator (the content of which is 3% of the molar mass of all monomers) to this solution, mix it well and heat it to 80 ° C, and keep it for about 6 hours. Then, a large amount of methanol was added to the reaction solution to generate crystals, and this was repeated three times to purify the crystal product. Drying gave 15.8 g of copolymerized product. After analysis, the reaction yield was 67.1%, and the weight average molecular weight of the polymerization product was 9,600. This copolymer is called Resin 200407668 A5. <Solvent> 26 parts 26 parts 3 parts 57 parts 3 parts E1: (propylene glycol monomethyl ether) acetate 2-heptanone T-butyrolactone E2: (propylene glycol monomethyl ether) acetate 7-butyrolactone Experiment 1 to 6 and control experiments 1 to 2; the following ingredients were mixed to prepare a solution, which was further filtered through a fluororesin filter with a pore size of 0.2 / zm to obtain a liquid photoresist. <Acid source> B1: 2,4,6-triisopropyl-3-nitro-benzenesulfonic acid (4-methyl) phenyldiphenylsulfide salt B2: 3,5-bis (2- Cyclohexylethoxycarbonyl) benzenesulfonic acid (4-methyl) phenyl-phenylthiosulfate B3: Perfluorooctanesulfonic acid p-methylphenyldiphenylsulfide salt <Resin> (type and content (See Table 1) <quenching agent>

Cl: 0.0075 parts of 2,6-diisopropylaniline <solvent> 33.25 parts of propylene glycol monomethyl ether acetate 33.25 parts of heptone 33.25 parts of r-butyrolactone 3.5 parts of each silicon wafer substrate is coated with Brewer The produced organic-41-200407668 anti-reflective coating is composed of "ARC-29A-8" and then baked at a temperature of 215 ° C for 60 seconds to form a layer of 780 angstrom organic anti-reflective coating. Using the spin coating method, the photoresist liquid prepared according to the above method was coated on the anti-reflection coating, and after drying, the thicknesses were 0.30 // m (Table 2) and 0.39 // m (Table 3 and Table 4). The silicon resist-coated silicon wafer was pre-baked for 60 seconds on a direct heating plate. The electric furnace was heated to the temperature shown in the "PB" column of Tables 1 and 3. Then use an ArF excimer stepper ("NSR ArF" manufactured by Nicon Corporation, which is NA = 0.55 in Tables 1 and 2, and NA = 0.55 in Tables 3 and 4 2 / 3 ring), and each silicon wafer formed with a photoresist film will be provided for line and space pattern exposure, while gradually changing the exposure. The exposed silicon wafer was held at the temperature indicated by "PEB" in Tables 1 and 3 for 60 seconds, and then developed in a solution containing 2.38% by weight of tetramethylhydroxyammonium for 60 seconds. Using a scanning electron microscope, a bright field pattern (bdght field pattern) developed on an organic anti-reflective film substrate can be observed. The results are shown in Table 2. The so-called "bright field pattern" herein refers to a pattern obtained through exposure and development through a reticle, wherein the reticle includes a chrome frame (light-shielding layer) and a A linear chromium layer (light-shielding layer) extending on a glass surface (light-transmitting portion) and extending inside the frame. Therefore, after exposure and development, the bright-field pattern is to remove the photoresist layer of the surrounding lines and the space pattern, while leaving a photoresist layer corresponding to the outer frame on the outside of the area where the photoresist layer is removed. Effective Sensitivity: -42- 200407668 Table 2: Indicated by exposure. After exposure through a 0.13 // m mask, the line pattern (light-shielding layer) and space pattern (light-transmitting layer) reached an exposure of 1: 1. In Table 4: It is represented by the exposure amount. After exposure through a 0.18 // m mask, the line pattern (light-shielding layer) and space pattern (light-transmitting layer) reached an exposure of 1_ · 1. Resolution: It indicates the minimum size of the space pattern separated by the line pattern under the exposure of the effective sensitivity. Table 1

Resin (parts) Acid source (parts) Quencher PB PEB Experiment 1 A1 / 10 B1 / 0.22 C1 130 ° C 125 ° C Experiment 2 A1 / 10 B2 / 0.27 C1 100 ° C 110 ° C Experiment 3 A2 / 10 B2 / 0.27 C1 130 ° C 120 ° C Control experiment 1 A1 / 10 B2 / 0.27 C1 140 ° C 120 ° C Table 2 Experiment number Sensitivity (mJ / cm2) Resolution (β m) Experiment 1 36 0.12 Experiment 2 48 0.12 Experiment 3 45 0.12 Control Experiment 1 78 0.12 -432004200668 Table 3

Resin (parts) Acid source (parts) Quencher PB PEB Experiment 4 A1 / 10 B3 / 0.20 C1 130 ° C 110 ° C Experiment 5 A2 / 10 B3 / 0.20 C1 130 ° C 110 ° C Experiment 6 A3 / 10 B3 / 0.20 C1 130 ° C 100 ° C Control experiment 2 A4 / 10 B3 / 0.20 C1 130 ° C 130 ° C Table 4 Experiment number Sensitivity (mJ / cm2) Resolution (/ zm) Experiment 1 17 0.16 Experiment 2 13 0.16 Experiment 3 26 0.16 Control Experiment 2 20 0.16 The chemically amplified positive photoresist composition of the present invention shows excellent sensitivity and excellent corrosion resistance such as resolution. Therefore, it is suitable for use in laser lithography techniques such as KrF, ArF, and has a large industrial price.

Claims (1)

200407668 Scope of patent application: 1. A resin containing a structural unit such as chemical formula (I): Here, R1 represents an alkylene group containing 1 to 4 carbon atoms, R2 represents an alkyl group containing 1 to 4 carbon atoms, and R3 represents hydrogen or methyl. 2. A chemically amplified positive photoresist composition including a resin containing a first structural unit of formula (I), (I) where R1 represents an alkylene group containing 1 to 4 carbon atoms, R2 represents an alkyl group containing 1 to 4 carbon atoms, and R3 represents hydrogen or methyl group, the resin itself is insoluble or slightly soluble in an alkaline solution, However, it is soluble in alkaline solvents after reacting with acid or an acid-producing source. -45- ^ υυ4〇7668 3. The chemically amplified positive photoresist composition described in item 2 of the scope of patent application, wherein the content of the first structural unit of the chemical formula (I) is the molar ratio of the resin. 4. The chemically amplified positive photoresist composition described in item 2 of the scope of the patent application, wherein the resin further includes at least a second structural unit selected from the group consisting of (meth) acrylic acid 3- Structural unit of hydroxy-1-adamantine ester, structural unit derived from 3,5-dihydroxy-1-adamantane methacrylate, derived from methacryloyloxy-7-butyrolactone (lactone can be One of the structural units of chemical formula (na) and (nb), R4 and R6 represent hydrogen or methyl, R5 and R7 represent methyl, and n represents an integer between 0 and 3. 5. The chemically amplified positive photoresist composition described in item 2 of the scope of the patent application, wherein the resin is further derived from the structural unit of norbornyl and the structural unit of aliphatic unsaturated dicarboxylic anhydride. 6. The chemically amplified positive photoresist composition according to item 2 of the scope of the patent application, wherein the acid generating source is selected from a sulfur key salt containing a chemical formula (Ha) -46- 200407668 Among them, P1 to P3 represent hydrogen, hydroxyl, alkyl or alkoxy group having 1 to 6 carbon atoms, and ζ · represents an anion and an iodine key salt of the chemical formula (nb). Among them, P4 and P5 respectively represent hydrogen, hydroxyl, and a radical or a radical containing 1 to 6 carbon atoms, and Z- represents an anion or a sulfur key salt S + —CH ^ C- ^ P9 Z ( IIIc) P6, P7 / &gt; θ where ρ6 and ρ7 respectively represent a radical containing 1 to 6 carbon atoms or a cycloalkyl group containing 3 to 10 carbon atoms, or a bond between P and P7 to form a compound containing 3 to 7 Divalent aliphatic hydrocarbons of one carbon atom, which in turn form a ring with adjacent S +, and at least one of the divalent aliphatic hydrocarbons -CH2- may be replaced by -CO ·, -0 or -S_, P8 represents a hydrogen atom, P9 represents an alkyl group containing 1 to 6 carbon atoms, a cycloalkyl group containing 3 to 10 carbon atoms, or a substituted aromatic compound, or P8 is bonded to P9, and then is adjacent to -CHCO -Formation of a 2-oxocycloalkyl group, Z_ represents an anion. 7. The chemically amplified positive photoresist composition as described in item 6 of the patent application scope, wherein Z- is an anion of the chemical formula (IV) 47- 200407668 Among them, Q1 to Q5 represent hydrogen, an alkyl or alkoxy group containing 1 to 16 carbon atoms, halogen, an aryl group containing 6 to 12 carbon atoms, an aralkyl group containing 7 to 12 carbon atoms, and a nitrile, respectively. Group, sulfide, hydroxyl, nitro, or a group of the formula (I ') ^ COOX—Cy1 Cl') In the formula, X represents an alkylene group, and at least one of the alkylene groups -ch2- is replaced by-. -Or substituted, Cy1 represents an alicyclic hydroxyl group containing 3 to 20 carbon atoms. 8. The chemically amplified positive photoresist composition as described in item 2 of the patent application scope, wherein the content of the resin accounts for 80% to 99.9% of the total weight of the resin and the acid generating source, and the content of the acid generating source is It accounts for 0.1% to 20% of the total weight of the resin and the acid generating source. 9. The chemically amplified positive photoresist composition according to item 2 of the scope of patent application, wherein the composition further includes a basic nitrogen-containing organic compound as a quencher. 10. The chemically amplified positive photoresist composition according to item 9 of the scope of the patent application, wherein the content of the basic nitrogen-containing organic compound accounts for 0.001% to 1% by weight of the resin. -48- 200407668 R1 represents alkylene having 1 to 4 carbon atoms, R2 represents alkyl having a to 4 carbon atoms, and R3 represents hydrogen or methyl, and also provides a chemical amplification type positive resist composition comprising a resin defined above and an acid generator. 柒, Designated representative map ... (1) The designated representative map in this case is: (No picture). (2) Brief description of the representative symbols of the components in this representative map: If there is a chemical formula in the case of support or proposal, please disclose the chemical formula that can best show the characteristics of the invention: